CN108384079A - A kind of preparation method of nitrile rubber corrugation gloves - Google Patents
A kind of preparation method of nitrile rubber corrugation gloves Download PDFInfo
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- CN108384079A CN108384079A CN201810162665.0A CN201810162665A CN108384079A CN 108384079 A CN108384079 A CN 108384079A CN 201810162665 A CN201810162665 A CN 201810162665A CN 108384079 A CN108384079 A CN 108384079A
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- butyronitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/015—Protective gloves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic System
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
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- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
- C08J2309/04—Latex
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Abstract
Wrinkle the preparation methods of gloves the present invention relates to a kind of nitrile rubber, is the first impregnation in butyronitrile wrinkles rubber cement by gloves embryos, then immerse in surface treatment finish and be surface-treated, finally vulcanization drying is made；Wherein butyronitrile corrugation rubber cement is made by the following method：90~120 parts of NBR latexes of weight meter, 1~6 portion of activating agent, 0.5~4 part of vulcanization accelerator, 1~5 part of vulcanizing agent are mixed, parked at least 1 day, thickener is added and is thickened to predetermined viscosity, is prepared into butyronitrile corrugation rubber cement；It includes 90 120 part of first finish of weight meter, 10~40 part of second finish and 1~5 part of third finish to be surface-treated finish, which is the organic solvent for having swelling action to nitrile rubber, which is low-carbon alcohols, which is organic acid.The nitrile rubber corrugation gloves prepared according to the method for the present invention, compared to day latex corrugation gloves, the two has close non-skid property, and has in terms of oil resistant, heat-resisting, corrosion-resistant, wearability than existing butyronitrile gloves and be obviously improved, up to the wear-resisting class 4 grades of EN388.
Description
Technical field
The present invention relates to a kind of preparation method of butyronitrile gloves, especially a kind of preparation side of nitrile rubber corrugation gloves
Method.
Background technology
Current safety and industrial gloves is various in style, some kinds require opponent because of special requirement (if you need to increasing friction force)
The glue surface of set carries out necessary processing.Presently commercially available wrinkle gloves are mostly natural emulsion class wrinkle gloves, but natural emulsion class
Wrinkle gloves are all apparent insufficient in terms of its oil resistivity, wear-resisting property although antiskid effect is preferable.Since NBR latex is
A kind of latex that polarity is larger, it is difficult to find suitable for production application, can Fast-swelling nitrile rubber finish, therefore be difficult
Wrinkle.Therefore, commercially available butyronitrile safety and industrial gloves, surface are mostly smooth surface, and antiskid effect is very poor, though there is its part of some gloves through surface
Processing forms frosted gloves, but its complex manufacturing technology, seriously polluted.Butyronitrile frosted gloves are by passing through in gloves glue surface
What spray salt and washing process were made.This kind of gloves are all made using conventional method, specifically first by NBR latex, water
Property polyurethane and polychloroprene latex, emulsifier, ball milling material, water or dilute alkaline aqueous solution match butyronitrile frosted slurry be made, will be through coagulator
The gloves of impregnation are immersed in butyronitrile frosted slurry and after carrying out homogenized, then spray sodium chloride or sodium sulphate to glue surface
After layer, progress presulfurization drying, then soaked cleaning is carried out repeatedly to presulfurization defensive position set and forms frosting, making frosted gloves.
This method needs first to prepare butyronitrile frosted slurry using a variety of dispensings such as ball milling material, and sprays salt (sodium sulfate salt or sodium chloride) mistake
Journey, makes workshop air by dust pollution, and harmful effect is caused to shop personnel's body, the quilt that soaked cleaning generates in addition
The water body of sodium sulphate pollution, brings pollution to waste the problems such as big.In addition, although this kind of gloves manufactured goods oil resistivity is strong to cross genuine milk
Rubber gloves, but its frictional force and oil resistivity also need to be further increased.In short, butyronitrile gloves have corrugation difficult, frictional force and resistance to
The still insufficient problem of oiliness.
Invention content
In order to solve the above problem of the prior art, the present invention provides a kind of preparation method of nitrile rubber corrugation gloves,
The method of the present invention mainly during preparing butadiene-acrylonitrile cement, by selecting the ratio of suitable material and reasonable design, is adjusted
With butyronitrile wrinkles rubber cement, and just there is the surface treatment finish of special formulation to be surface-treated after gloves embryo impregnation, be made
Nitrile rubber corrugation gloves.
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of preparation method of nitrile rubber corrugation gloves, the method first soak gloves embryo in butyronitrile wrinkles rubber cement
Glue, then immerse in surface treatment finish and be surface-treated, nitrile rubber corrugation gloves are made in finally vulcanization drying；Wherein butyronitrile
Corrugation rubber cement is made by the following method：By weight by 90~120 parts of NBR latexes, 1~6 portion of activating agent, 0.5~4 part of sulphur
Change accelerating agent, 1~5 part of vulcanizing agent mixing, parks at least 1 day, thickener is added and is thickened to predetermined viscosity, be prepared into butyronitrile corrugation
Rubber cement；The surface treatment finish includes the first finish of weight meter 90-120 parts, 10~40 part of second finish and 1~5 part of third
Finish, first finish are the organic solvents for having swelling action to nitrile rubber, which is low-carbon alcohols, the third finish
It is organic acid.
Vulcanization accelerator accelerator ' the promoter used in butyronitrile corrugation rubber cement are prepared, for improving reaction speed
A kind of less substance of dosage of rate, can be used as the curing agent of reinforced resin, improves the hardness of rubber product.Vulcanization accelerator letter
Claim accelerating agent, promotes the substance of sulfurization.Using vulcanization accelerator, can effectively shorten rubber vulcanization time or reduce vulcanization
Temperature reduces vulcanizing agent dosage and improves the physical mechanical property etc. of rubber.Vulcanization accelerator can be divided into inorganic accelerator and have
Machine accelerating agent two major classes.Organic accelerator is mainly nitrogenous and sulfur-bearing organic compound, there is aldehyde amines (such as vulcanization accelerator
H), guanidine (such as accelerator D), thiurams (such as vulcanization accelerator TT), thiazoles (such as accelerator M), two thio
Carbamates (such as accelerator ZDMC), xanthic acid salt (such as accelerator ZBX), Thiourea are (as vulcanization promotes
Agent NA-22), sulfenamide (such as accelerator CZ).It can be used alone or as a mixture as the case may be.
Preferably, the vulcanization accelerator is dithiocarbamates, thiurams, thiazoles, guanidine, Thiourea
Etc. a combination of one or more.
Specifically, the vulcanization accelerator is diphenylguanidine (diphenylguanidine C13H13N3), DETU (diethyl thiourea C5H12N2S)、
DPG (1,3- diphenylguanidine), M (2-mercaptobenzothiazole C7H5NS2), TMTD (thiuram C6H12N2S4), BZ (dibutyl dithio ammonia
Base zinc formate C18H36N2S4Zn), PZ (zinc diethyl dithiocarbamate C6H12N2S4Zn), ZDC (diethyl-dithio amino
Zinc formate C10H20N2S4) and CZ (N- cyclohexyls -2-[4-morpholinodithio sulfenamide C Zn13H16N2S2) one kind or aforementioned every
Arbitrary combination.
The activating agent used in butyronitrile corrugation rubber cement is prepared, the effect in butyronitrile wrinkles rubber cement includes mainly that (1) activates
Vulcanizing system；(2) crosslink density of vulcanizate is improved；(3) ageing-resistant performance of vulcanizate is improved.In addition, activator can also fill
Organic accelerator effect is waved in distribution, reduces dosage/shortening vulcanization time.Wherein activator ZnO2Effect is in addition to sulfurate activity
Effect is outer, also vulcanization/reinforcement/compatibilization.
In an embodiment of the invention, activating agent is one kind or aforementioned each in zinc oxide, zinc carbonate and zinc stearate
The arbitrary combination of item.Wherein, the activating agent can be used alone, and can also be used in mixed way, and zinc oxide accounts for 80% or so when mixing, firmly
Resin acid zinc 20% or so or zinc carbonate 80% or so and zinc stearate 20% or so.Zinc oxide, zinc stearate, zinc carbonate etc.
Activating agent is used to promote the formation of polymer molecular chain covalent bond or ionic bond, to help to make in the intermolecular bridge formation that plays of line style
With being cross-linked into network structure to make multiple linear molecules be mutually bonded.Therefore, by the promoter effect of activating agent, system can be made
The rubber of product has the performances such as preferably wear-resistant and chemicals-resistant.
In the application, vulcanization is the technical process for instigating linear rubber molecule to be cross-linked to form dimensional network structure.And sulphur
Agent refers to all substances that linear rubber molecule can be made to be cross-linked to form dimensional network structure, including sulphur, heating temperature
Down the compound of releasable sulfur-containing radicals and other rubber molecule can be made to be cross-linked to form the not sulfur-containing compound of network structure
(including resin curing agent).
In an embodiment of the invention, the vulcanizing agent is one or more of combinations of sulphur, thiurams.It is described
Thiurams is thiuram-disulfide or thiurampolysulfides.Both thiurams at a temperature of standard cure because that can release work
Property sulphur or sulfur-containing radicals, therefore can be used as vulcanizing agent use.Therefore, sulphur, thiuram-disulfide, more sulphur can be used in the present invention
Change the group of thiuram, sulphur+thiuram-disulfide, sulphur+thiurampolysulfides or thiuram-disulfide and thiurampolysulfides
It closes.
I.e. room temperature is parked, by parking for room temperature long period, the part presulfurization of NBR latex linear molecule can be made
(slight vulcanization), and presulfurization result is made to be uniformly distributed in rubber cement.Wherein, in butyronitrile corrugation rubber cement preparation process, when parking
Between preferably 2~3 days.
According to one embodiment of present invention, when preparing the butyronitrile corrugation rubber cement, crosslinking agent is also added, crosslinking agent
It is 0~5 part to add number；The crosslinking agent is that aziridines, polyalcohols, polynary amine are a kind of or every arbitrary group aforementioned
It closes；The polynary amine includes propane diamine, to two o-chloraniline methane；The polyalcohols include polyethylene glycol, polypropylene glycol,
Trimethylolpropane.
When preparing butyronitrile corrugation rubber cement, vulcanizing agent can make a part of active group of linear rubber molecule by vulcanizing agent
And be connected with each other, dimensional network structure is formed, sulfurate activity point is mainly acted on；The effect of crosslinking agent is to another part
It is not suitable for the active group bridged by vulcanizing agent, network structure is connected by crosslinking agent, mainly acts on crosslinking active base
Group.Vulcanizing agent and crosslinking agent, the two play the role of complementary mutual assistance in butyronitrile wrinkles rubber cement, and purpose is all to promote nitrile rubber
Newborn molecule forms dimensional network structure, to make product have desired oil resistivity and wearability.In addition, preparing butyronitrile corrugation
When rubber cement, vulcanizing agent additive amount is less, and temperature is relatively low, it is ensured that butyronitrile wrinkle rubber cement be not complete cure state, to for
The swelling action that back side surface handles finish forms wrinkle offer precondition.
Chemical bond linkage between each segment of macromolecule is crosslinking.Crosslinking agent can make linear molecule be cross-linked with each other into network knot
Structure.Crosslinking agent is used primarily in high molecular material, because the line that the molecular structure of high molecular material is grown as a rule, is not crosslinked
Shi Qiangdu is low, easily breaks, and without elasticity, and the effect of crosslinking agent is exactly to generate chemical bond between the molecule of line style, makes line style
Molecule is connected with each other, and is formed reticular structure, is improved the intensity and elasticity of rubber.In the application, used crosslinking agent is
Outside cross-linking agent is also curing agent, curing agent, it can make line style or the macromolecular of slight branched chain type be transformed into tridimensional network,
The performances such as intensity, heat resistance, wearability, solvent resistance are improved with this, can be used for foaming or not foaming product.
According to one embodiment of present invention, when preparing the butyronitrile corrugation rubber cement, foaming agent is also added, foaming agent
It is 0~3 part to add number, is prepared into expansion type butyronitrile corrugation rubber cement；The foaming agent is potassium oleate, enuatrol, dodecyl
One kind in the anion surfactants such as benzene sulfonic acid sodium salt, lauryl sodium sulfate and potassium laurate is every arbitrary group aforementioned
It closes.These anion surfactants can make the expansion type butyronitrile rubber being prepared for cationic surfactant
Glue is more stable.
According to one embodiment of present invention, the usage amount of the thickener is 0.2~6 part；Preferably, the thickener
For sodium carboxymethylcellulose CMC, hydroxymethyl ethylcellulose, hydroxyethylpropyl cellulose, Sodium Polyacrylate, polyacrylic acid, do
The arbitrary combination of one kind or aforementioned items in casein, PVAC polyvinylalcohol.By thickener by butyronitrile wrinkle rubber cement formulated viscosity
To 1800mpa.s~2500mpa.s.After the viscosity of butyronitrile corrugation rubber cement determines gloves embryo impregnation, it is stranded in gloves embryo surface
The thickness and product rubber thickness of glue-line, thus in actual production can carry out formulated viscosity to required according to the thickness of needs
Value.But when needing to form corrugated side, due to subsequently to pass through the processing of surface treatment finish, in allotment butyronitrile corrugation
The viscosity of rubber cement can be appropriate higher such as 2000mpa.s~2500mpa.s, in case glue-line is perforated.
According to one embodiment of present invention, first finish is toluene, dimethylbenzene, chloroform, dichloromethane and acetone
One kind or aforementioned items arbitrary combination.First finish predominantly has the organic molten of stronger swelling action to nitrile rubber
Agent, it is main to play a part of to dissolve colloid outside gloves embryo.The swelling action reaction result of vulcanization and unvulcanized rubber to solvent
It is different.It can be dissolved after the swelling of unvulcanized rubber, and only generating body swollen for vulcanized rubber, will not dissolve.Therefore, this hair
It is bright prepare butyronitrile wrinkle rubber cement during, less amount of vulcanizing agent (1~5 part of vulcanizing agent) is only added, makes nitrile rubber only
Partial vulcanization occurs, and unvulcanized nitrile rubber occurs just with the contact process of surface treatment finish (swelling finish)
Swelling dissolves and is partially stripped phenomenon, and vulcanized rubber then will not be in this way, so that finally film surface occurs outside gloves embryo
Crepe structure.
It is usually the organic solvent of the strong solubility of nonpolar (nonpolarity) to have the organic solvent of swelling action to rubber, such as
Chloroform, chloroform, carbon tetrachloride, toluene, dimethylbenzene, acetone etc..
In an embodiment of the invention, the second finish of the surface treatment finish is methanol, ethyl alcohol, propyl alcohol etc. 10
One kind in carbon low-carbon alcohols below or arbitrary combination；Second finish is demulsification finish, mainly plays demulsification (alcohols finish side
It is demulsified again, alcohols finish also has certain freezing action).
In an embodiment of the invention, the third finish of the surface treatment finish is formic acid, acetic acid, benzoic acid, benzene
One or more of combinations of the organic acids such as acetic acid；Third finish mainly plays freezing action.Organic acid and the latex of alkalinity occur
Acid-base neutralization reaction promotes the effect of solidification glue surface.
In an embodiment of the invention, the dip time for being surface-treated finish is 2~5 seconds, makes gloves glue surface in the table
Under the multiple actions such as swelling, demulsification and the solidification of surface treatment finish, corrugation rough surface is formed on gloves glue surface surface, then through vulcanization
Drying is prepared into nitrile rubber corrugation gloves.
In one embodiment of the invention, vulcanization drying and processing includes mainly first cryogenic vulcanization drying and high temperature vulcanized again
Dry two stages.Preferably, 65~85 DEG C of 30~45min of time of the cryogenic vulcanization drying temperature；The high temperature vulcanized temperature
Spend 100~120 DEG C of 60~90min of time.
Vulcanization drying, which is divided into the benefit in two stages, is：Since latex film forming process is slower, to pass through tightly packed
Process, if start just using high temperature vulcanized, it is easy to so that the surface quick film-forming of product is fine and close, and inside due to moisture compared with
It is more, it causes steam that can not be discharged, can only be formed and be bubbled in product surface, cause serious product defects, especially latex dipping
Class thick product, it is therefore desirable to first pass through cryogenic vulcanization (≤85 DEG C) 30 minutes or so, make product processing be easier, defect is avoided to produce
It is raw；Then high temperature vulcanized (≤100 DEG C are carried out) 60 minutes or more, reach product performance and production standard.
In an embodiment of the invention, the gloves embryo be chemical fibre knitted gloves embryo or cotton interlock gloves embryo, when for change
When fine knitted gloves embryo, the chemical fibre knitted gloves embryo further includes a dipping solidification before impregnation in butyronitrile wrinkles rubber cement
The pre-treatment step of agent, the coagulator are the alcoholic solution of the alcoholic solution of calcium chloride, calcium nitrate alcoholic solution or zinc chloride, the alcohol
To be the alcohol of liquid under the room temperature such as methanol, ethyl alcohol, propyl alcohol, gloves embryo temperature is 45~55 DEG C when impregnating coagulator.
Chemical fibre knitted gloves blastopore hole is larger, and such as without the processing of pre-soaked coagulator, when can lead to impregnation, sizing material oozes
Thoroughly on the inside of gloves embryo (side contacted with skin of hand), user is uncomfortable, product is nonconforming.And the hole of cotton interlock gloves
Hole very little, generally will not there is a situation where penetrate into inside after impregnation.When impregnating coagulator, gloves embryo requires heat to a constant temperature
Degree, can so help the alcohol (alcohol of liquid under the room temperature such as methanol or ethyl alcohol) in coagulator that can quickly volatilize away, otherwise
If gloves temperature when immersing in coagulator is too low, alcohol liquid is difficult to wave to send out in time, and follow-up impregnation will appear when processing
Drop wears, seep through, or a series of problems, such as decortication, so gloves embryo will have a certain temperature when dipping coagulator, preferably 45 DEG C~
55℃。
The beneficial effects of the invention are as follows：
The present invention prepare butyronitrile wrinkle rubber cement when, select appropriate deal NBR latex and vulcanizing agent, assistant with appropriate part
Butyronitrile corrugation rubber cement is prepared after parking presulfurization in the activating agent and vulcanization accelerator of amount；Simultaneously as needed, may be used also
To add crosslinking agent during preparing butyronitrile corrugation rubber cement, it is used cooperatively with vulcanizing agent, crosslinking agent is mainly used for vulcanizing agent
Cannot act on active site (including vulcanizing agent additive amount it is less and what the sulfurate activity point and vulcanizing agent that cannot act on did not acted on
Unvulcanised active site) crosslinked action is played, further increase the oil resistivity and wearability of product.After gloves embryo impregnation, use
The surface treatment finish being made of the first finish, the second finish and third finish, is swollen the glue-line of gloves embryo surface, is broken
, there is crepe structure in film surface in breast and the solidifying processing of rush, are most prepared into the nitrile rubber corrugation through vulcanizing drying and processing afterwards
Gloves.
Test and comparison is found, according to the nitrile rubber corrugation gloves of the method for the present invention preparation, compared to day latex corrugation hand
Set, the two have close non-skid property；And the nitrile rubber of the present invention wrinkles gloves while taking into account non-skid property,
Have in terms of oil resistant, heat-resisting, corrosion-resistant, wearability relative to existing butyronitrile gloves and is obviously improved.After tested, preparation
Nitrile rubber wrinkles gloves up to the wear-resisting class 4 grades of EN388 (European standard), and overall performance is excellent.
Description of the drawings
Fig. 1：For the photo of butyronitrile corrugation gloves prepared by present pre-ferred embodiments 1.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, foaming agent neopelex is added, 1.2 times of foaming is thickened with CMC (mass fraction 2%)
To 2000mpa.s, it is fabricated to butyronitrile corrugation rubber cement.Its described each component adds mass fraction：100 parts of NBR latex, activity
4 parts of agent zinc oxide, 2 parts of vulcanization accelerator ZDC (zinc diethyl dithiocarbamate), 1 part of sulphur, crosslinking agent aziridines 2
Part, 1.5 parts of foaming agent neopelex, 3 parts of 2%CMC.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 50 DEG C, the calcium nitrate methanol soln for immersing 2% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 2 minutes
(drop glue is placed).
Step S3, it is surface-treated：100 parts of dimethylbenzene, 30 parts of methanol and 2 parts of acetic acid are mixed by weight, matched
Surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 2~
It is taken out after 5 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 40min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
As shown in Figure 1, the photo for the gloves that wrinkle for the butyronitrile that the present embodiment is prepared into, can be clearly seen that hand by the photo
Set rubber surface has having many bends or curves irregular wrinkle lines, these lines that can be effectively increased the frictional force of the gloves, meets production
Labour needs, and relative to natural emulsion corrugation gloves, nitrile rubber corrugation gloves have absolutely excellent in oil resistivity, corrosion resistance
Gesture.
Embodiment 2
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 2 days, 2500mpa.s is thickened to casein, be fabricated to butyronitrile corrugation rubber cement.Its described each component addition
Mass fraction is：120 parts of NBR latex, 6 parts of activating agent zinc carbonate, accelerator D (diphenylguanidine C13H13N3) 4 parts, sulphur 2
Part, 5 parts of polyalcohols crosslinking agent, 6 parts of casein, are parked 2 days at room temperature, and non-foamed type butyronitrile corrugation rubber cement is made.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 55 DEG C, the calcium chloride methanol solution for immersing 4% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 2 minutes.
Step S3, it is surface-treated：120 parts of chloroform, 40 parts of ethyl alcohol and 5 parts of benzoic acid are mixed by weight, matched
Surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 3~
It is taken out after 4 seconds.
Step S4, vulcanization drying：By product among gloves first at 65 DEG C, cryogenic vulcanization dries 45min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 80min, butyronitrile corrugation gloves are made.
Embodiment 3
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, foams to 1.3 times, after parking 3 days, 2200mpa.s is thickened to PVA, be fabricated to butyronitrile corrugation rubber cement.It is wherein described
Each component adds mass fraction：90 parts of NBR latex, the 1 part of (zinc oxide of activating agent mixed：Zinc stearate=4:1 weight),
Vulcanization accelerator TMTD (thiuram C6H12N2S4) 0.5 part, 1 part of sulphur, 3 parts of foaming agent potassium laurate, thickener polyvinyl alcohol 5
Part, it parks at room temperature 3 days, obtains expansion type butyronitrile corrugation rubber cement；
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 45 DEG C, the zinc chloride ethanol solution for immersing 5% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 3 minutes.
Step S3, it is surface-treated：90 parts of acetone, 10 parts of propyl alcohol and 1 part of formic acid are mixed by weight, with obtained
It is surface-treated finish, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 2~3 seconds
After take out.
Step S4, vulcanization drying：By product among gloves first at 80 DEG C, cryogenic vulcanization dries 30min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
Embodiment 4
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, 2300mpa.s is thickened to hydroxyethylpropyl cellulose, be fabricated to butyronitrile corrugation rubber cement.Described in it
Each component adds mass fraction：120 parts of NBR latex, 5 parts of activating agent zinc oxide, accelerator D PG (1,3- diphenylguanidine) 5
Part, 5 parts of sulphur, 6 parts of hydroxyethylpropyl cellulose.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 50 DEG C, the calcium chloride methanol solution for immersing 5% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 2 minutes.
Step S3, it is surface-treated：110 parts of dichloromethane, 25 parts of ethyl alcohol and 4 parts of phenylacetic acid are mixed by weight
It closes, with surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating is entered into the surface treatment finish
In, it is taken out after 3~4 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 40min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
Embodiment 5
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, foaming agent lauryl sodium sulfate is added, 1.2 times of foaming is thickened to CMC (mass fraction 2%)
2000mpa.s is fabricated to butyronitrile corrugation rubber cement.Its described each component adds mass fraction：100 parts of NBR latex, activating agent
3 parts of zinc oxide, accelerator M (2-mercaptobenzothiazole C7H5NS2) 2.5 parts, 3 parts of thiurams vulcanizing agent, 0.5 part of sulphur,
Polynary 3 parts of amine (propane diamine) crosslinking agent, 0.5 part of foaming agent neopelex, 4 parts of 2%CMC.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 50 DEG C, the calcium nitrate methanol soln for immersing 2% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 3 minutes.
Step S3, it is surface-treated：100 parts of chloroform, 20 parts of methanol and 4 parts of benzoic acid are mixed by weight, matched
Surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 2~
It is taken out after 5 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 40min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
Embodiment 6
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, foaming agent potassium oleate is added, 1.1 times of foaming is thickened to CMC (mass fraction 2%)
2000mpa.s is fabricated to butyronitrile corrugation rubber cement.Its described each component adds mass fraction：100 parts of NBR latex, activating agent
2 parts of zinc oxide, 1 part of vulcanization accelerator BZ (zinc dibutyl dithiocarbamate), 1 part of thiurams vulcanizing agent, 3 parts of sulphur,
Polynary 0.5 part of crosslinking agent of amine (to two o-chloraniline methane), 1 part of foaming agent potassium oleate, 5 parts of 2% sodium carboxymethylcellulose.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 50 DEG C, the calcium nitrate methanol soln for immersing 2% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 3 minutes.
Step S3, it is surface-treated：110 parts of dimethylbenzene, 35 parts of ethyl alcohol and 5 parts of phenylacetic acid are mixed by weight,
With obtained surface treatment finish, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 3
It is taken out after~5 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 40min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
Embodiment 7
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, foaming agent potassium laurate is added, 1.2 times of foaming is thickened to CMC (mass fraction 2%)
2000mpa.s is fabricated to butyronitrile corrugation rubber cement.Its described each component adds mass fraction：100 parts of NBR latex, activating agent
1 part of zinc oxide, accelerator P Z (C6H12N2S4Zn) 1 part, 4 parts of thiurams vulcanizing agent, 1 part of sulphur, polynary amine (the third two
Amine) 3 parts of crosslinking agent, 2 parts of potassium laurate, 4~5 parts of 2% sodium carboxymethylcellulose.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 50 DEG C, the calcium nitrate methanol soln for immersing 3% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 2 minutes.
Step S3, it is surface-treated：110 parts of chloroform, 30 parts of ethyl alcohol and 3 parts of benzoic acid are mixed by weight, matched
Surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating are entered in the surface treatment finish, 3~
It is taken out after 5 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 40min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 70min, butyronitrile corrugation gloves are made.
Embodiment 8
Step S1, butyronitrile corrugation rubber cement is prepared：Abrasive material (vulcanization accelerator, vulcanizing agent and activating agent) and NBR latex is mixed
It closes uniformly, after parking 3 days, foaming agent potassium oleate is added, 1.2 times of foaming is thickened to hydroxymethyl ethylcellulose
2200mpa.s is fabricated to butyronitrile corrugation rubber cement.Its described each component adds mass fraction：100 parts of NBR latex, activating agent
4 parts of zinc oxide, 3 parts of accelerator CZ (N- cyclohexyls -2-[4-morpholinodithio sulfenamide), 3 parts of thiurams vulcanizing agent, sulphur
2 parts, 2 parts of polyethylene glycol crosslinked agent, 1.5 parts of foaming agent potassium oleate, 4~5 parts of hydroxymethyl ethylcellulose.
Step S2, impregnation：By chemical fibre knitted gloves embryo when temperature is 45 DEG C, the calcium nitrate methanol soln for immersing 5% coagulates
Gu in agent, and carrying out after impregnating coagulator processing, then immerse in the butyronitrile corrugation rubber cement that step S1 is mixed up, then spin coating 2 minutes.
Step S3, it is surface-treated：105 parts of dichloromethane, 28 parts of ethyl alcohol and 3.5 parts of benzoic acid are mixed by weight
It closes, with surface treatment finish is made, product among the gloves after step S2 impregnations and spin coating is entered into the surface treatment finish
In, it is taken out after 3~5 seconds.
Step S4, vulcanization drying：By product among gloves first at 75 DEG C, cryogenic vulcanization dries 30min, finally in high temperature sulphur
Change at 110~120 DEG C of temperature, high temperature vulcanized drying 80min, butyronitrile corrugation gloves are made.
It wrinkles gloves according to the method manufacture nitrile rubber of embodiment 1-8, in oil resistant, wear-resisting, corrosion-resistant, heat-resisting aspect ratio
Existing butyronitrile gloves are more preferable, and non-skid property and existing natural emulsion corrugation gloves are close.After tested, the nitrile rubber of preparation
Gloves wrinkle up to the wear-resisting class 4 grades of EN388 (European standard).
Claims (10)
1. a kind of preparation method of nitrile rubber corrugation gloves, it is characterised in that：
The method be first by gloves embryo butyronitrile wrinkle rubber cement in impregnation, then immerse surface treatment finish in carry out surface at
Nitrile rubber corrugation gloves are made in reason, finally vulcanization drying；
The butyronitrile corrugation rubber cement is made by the following method：By weight by 90~120 parts of NBR latexes, 1~6 part of activity
Agent, 0.5~4 part of vulcanization accelerator, 1~5 part of vulcanizing agent mixing, park at least 1 day, thickener are added and is thickened to predetermined viscosity,
It is prepared into butyronitrile corrugation rubber cement；
The surface treatment finish includes the first finish of weight meter 90-120 parts, 10~40 part of second finish and 1~5 part of third oil
Agent, first finish are the organic solvents for having swelling action to nitrile rubber, which is low-carbon alcohols, which is
Organic acid.
2. preparation method according to claim 1, it is characterised in that：The vulcanization accelerator be diphenylguanidine, DETU,
The arbitrary combination of one kind of DPG, M, TMTD, BZ, PZ, ZDC and CZ or aforementioned items.
3. preparation method according to claim 1, it is characterised in that：The activating agent is zinc oxide, zinc carbonate and tristearin
The arbitrary combination of one kind or aforementioned items in sour zinc.
4. preparation method according to claim 1, it is characterised in that：The vulcanizing agent is one kind of sulphur, thiurams
Or several combination.
5. preparation method according to claim 1, it is characterised in that：Described park refers to room temperature；It parks 2~3 days.
6. preparation method according to claim 1, it is characterised in that：When preparing the butyronitrile corrugation rubber cement, also add
The addition number of crosslinking agent, crosslinking agent is 0~5 part；The crosslinking agent be aziridines, polyalcohols, polynary amine it is a kind of or
The arbitrary combination of aforementioned items.
7. preparation method according to claim 1 or 6, it is characterised in that：When preparing the butyronitrile corrugation rubber cement, also add
Add foaming agent, the addition number of foaming agent is 0~3 part, is prepared into expansion type butyronitrile corrugation rubber cement；The foaming agent is oleic acid
One kind in the anion surfactants such as potassium, enuatrol, neopelex, lauryl sodium sulfate and potassium laurate
Or the arbitrary combination of aforementioned items.
8. preparation method according to claim 7, it is characterised in that：The thickener is sodium carboxymethylcellulose CMC, hydroxyl
One in methylethylcellulose, hydroxyethylpropyl cellulose, Sodium Polyacrylate, polyacrylic acid, casein, PVAC polyvinylalcohol
Kind or aforementioned item arbitrary combination, by thickener by butyronitrile corrugation rubber cement formulated viscosity to 1800mpa.s~
2500mpa.s。
9. preparation method according to claim 1, it is characterised in that：First finish be toluene, dimethylbenzene, chloroform,
The arbitrary combination of one kind or aforementioned items of dichloromethane and acetone；Second finish is methanol, ethyl alcohol, propyl alcohol etc. 10
One kind in carbon low-carbon alcohols below or arbitrary combination；The third finish is that formic acid, acetic acid, benzoic acid, phenylacetic acid etc. are organic
One or more of combinations of acid.
10. preparation method according to claim 1, it is characterised in that：The vulcanization drying and processing includes first cryogenic vulcanization
Drying and again two stages of high temperature vulcanized drying；65~85 DEG C of 30~45min of time of the cryogenic vulcanization drying temperature；The height
100~120 DEG C of 60~90min of time of warm curing temperature.
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| CN113185624A (en) * | 2021-05-13 | 2021-07-30 | 山东星宇手套有限公司 | Environment-friendly water-based latex coagulant and preparation method of rubber coating product |
| CN113248764A (en) * | 2021-06-21 | 2021-08-13 | 山东星宇手套有限公司 | Rubber surface treating agent, preparation method and rubber surface treatment process |
| CN113248764B (en) * | 2021-06-21 | 2023-01-10 | 山东星宇手套有限公司 | Rubber surface treating agent, preparation method and rubber surface treatment process |
| CN113831558A (en) * | 2021-09-23 | 2021-12-24 | 汇鸿(南通)安全用品有限公司 | Preparation method of water-based butyl gloves without linings |
| CN114292452A (en) * | 2021-12-29 | 2022-04-08 | 山东星宇手套有限公司 | Rubber pitted surface dipping gloves and manufacturing method thereof |
| CN114292452B (en) * | 2021-12-29 | 2024-02-02 | 山东星宇手套有限公司 | Rubber pitted surface impregnated glove and manufacturing method thereof |
| CN114316392A (en) * | 2022-02-25 | 2022-04-12 | 天津市橡胶工业研究所有限公司 | Butyronitrile protective gloves with lining long sleeves and preparation method thereof |
| CN114316392B (en) * | 2022-02-25 | 2023-09-05 | 天津市橡胶工业研究所有限公司 | Inner lining-containing long-sleeve butyronitrile protective glove and preparation method thereof |
| CN114854057A (en) * | 2022-04-26 | 2022-08-05 | 濮阳林氏医疗制品有限公司 | Low-temperature vulcanization package group and preparation method and application thereof |
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